WO2004011475A1 - Derives de polyaminomethylenephosphonate - Google Patents

Derives de polyaminomethylenephosphonate Download PDF

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Publication number
WO2004011475A1
WO2004011475A1 PCT/IT2003/000420 IT0300420W WO2004011475A1 WO 2004011475 A1 WO2004011475 A1 WO 2004011475A1 IT 0300420 W IT0300420 W IT 0300420W WO 2004011475 A1 WO2004011475 A1 WO 2004011475A1
Authority
WO
WIPO (PCT)
Prior art keywords
polyaminomethylenephosphonate
derivatives
hydrogen
suitable cation
group
Prior art date
Application number
PCT/IT2003/000420
Other languages
English (en)
Inventor
Massimo Paladini
Francesco Spini
Alessandro Scalvedi
Daniele Tarallo
Jean Claude Valle
Original Assignee
Giovanni Bozzetto S.P.A.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Giovanni Bozzetto S.P.A. filed Critical Giovanni Bozzetto S.P.A.
Priority to AU2003281668A priority Critical patent/AU2003281668A1/en
Priority to EP03741094A priority patent/EP1525206B1/fr
Priority to US10/522,858 priority patent/US7087781B2/en
Priority to AT03741094T priority patent/ATE441655T1/de
Priority to DE60329109T priority patent/DE60329109D1/de
Publication of WO2004011475A1 publication Critical patent/WO2004011475A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/02—Polyamines
    • C08G73/0206—Polyalkylene(poly)amines
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
    • C02F5/08—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents
    • C02F5/10—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances
    • C02F5/14—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances containing phosphorus
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
    • C07F9/3804—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)] not used, see subgroups
    • C07F9/3808—Acyclic saturated acids which can have further substituents on alkyl
    • C07F9/3817—Acids containing the structure (RX)2P(=X)-alk-N...P (X = O, S, Se)

Definitions

  • the present invention relates to a new class of phosphonates and related salts, the method of preparation of the same and their utilization in the preparation of water additives to be used in different industrial fields. More particularly, the present invention relates to the preparation of products that impart to the water the particular characteristics needed for its utilisation. More specifically, the products and the processes according to the present invention make available new additives that prevent the segregation of solids from their aqueous solutions or dispersions acting as precipitation inhibitors and dispersants.
  • Salts showing this phenomenon are generally formed by earth-alkali metals (Ca; Ba; Mg); among thera Calcium - mostly as carbonate but also as sulfate -- is the main responsible for the phenomena of incrustation in several industrial water applications.
  • the incrustation ( not only limited to poory soluble salts ) is generally called " SCALE " by water treatment experts.
  • HCO 3 soluble bicarbonate
  • the causes are different and can be classified as follows'
  • the incrustation (scale) formation mechanism can be attributed to precipitation of salts from supersaturated solutions in the region adjacent to the heat exchange surface of the system.
  • incrustation facilitates the incorporation of solid particles that cannot be chemically removed (e.g. Si ⁇ 2) or the growth of bacteria and algae.
  • pretreatments have been proposed: they provide for the preventive elimination of low-solubility salts by ionic exchange, precipitation,or by the use of suitable "sequestering agents" and suitable " scale inhibitors".
  • Threshold Effect The Threshold Effect was discovered by observing the behaviour of inorganic polyphosphates that prevent the precipitation of the CaCO from supersaturated
  • the mechanism by which the precipitation is inhibited is not completely understood today, although the adsorption of inhibitor onto the crystalline surface seems necessarily to be the first step in the inhibition process.
  • the molecules of inhibitor are attracted on the growing crystalline surface by the presence of metal cations such as Ca, Mg, Ba for which they have a great affinity.
  • the inhibitor can disturb nuclear growth to such an extent as to make the nucleus redissolve.
  • the present invention relates to a new class of phosphonates, to a simple and economic process for the production of said new class of phosphonates and to the use of said phosphonates in water treatment applications. Therefore, the main object of the present invention is a new class of phosphonates that can be used for water treatment.
  • the compounds that form the object of the present invention are the derivatives of polyaminomethylenephosphonates having the following general formula:
  • n is an integer between 2 and 15000 preferably between 2 and 50;
  • M 2 may be hydrogen or a suitable cation and each R group may be a - CH 2 -PO 3 M2, group or a linear or
  • R 1 may be H, CH 3 , CH 2 C1, CH 2 OH
  • R is an alkyl with the number of carbon atoms between 3 and 5.
  • the compounds that form the object of the present invention are the derivatives of polyaminomethylenephosphonates according to the above mentioned formula where the polyamine chain may be linear or branched, and where n is an integer or fractional integer which is, or on average is, from about 2 to about 15000 :
  • M 2 may be hydrogen or a suitable cation such as alkali metal or ammonium, and where each R group my be the same or different and is independently selected from the following classes:
  • a particular advantage of this new class of phosphonates, object of this invention, is that such compounds do not show "Turbidity Zone" and are therefore to be considered non Calcium- sensitive at any concentration and temperature tested; they are also effectives at high pH values (>10).
  • Threshold Effect typical of the phosphonates, i.e. inhibition of precipitation from solutions supersaturated with CaCO and/or CaSO at sub-stoichiometric concentrations of
  • Non calcium-sensitivity increases in pH and concentration of calcium strongly affect the tolerance of the standard phosphonates (HEDP, ATMP, etc.) to calcium, increasing the possibility of precipitation of poorly soluble calcium-phosphonate salts.
  • Dispersing Effect better than the traditional phosphonates. This new class of phosphonates behaves like the acrylic polymers. They act as dispersants and deflocculants, stabilizing colloidal systems which remain steadily dispersed for long periods.
  • the products object of the present invention shows high "dispersing ability”.
  • HAMPSHIRE method: with this method it is not possible to identify an end-point during the titration with calcium acetate.
  • this property suggests a potential application of this new class of phosphonates as deflocculants, in a certain number of processes and applications where they are involved as stabilizers for different kind of dispersions like pigments (TiO2), kaolin and drilling mud stabilizers for different kind of dispersions like pigments ( ⁇ Q2), kaolin and drilling mud and in the industrial and domestic detergent field for their ability to disperse dirt particles.
  • the products according to the present invention can be used for:
  • sanitary cleaners paints; sec ⁇ dnary oil recovery; oil drilliflg muds; laundry detergents; industrial cleaners; peroxide stabilisation; metal finishing; metal cleaners; geothermal water; set retarde ⁇ s for concrete - car wash;
  • Obyect of the present invention is also a simple and economic process for the preparation of the phosphonates and their utilisation in the abovesaid fields, particularly as inhibitors of the formation, deposition, and adhesion of incrustations caused by insoluble salts of alkali-earth
  • metals in particular Ca , Mg ++ , on metal surfaces of aqueous systems (cooling towers, boilers, gas scrubbers etc.)
  • the compounds object of this invention is prepared by phosphonomethylation reaction of polyamine or mixtures of polyamines, by means of the Mannich reaction illustrated hereunder.
  • a typical procedure provides for the amine to be slowly added to a mixture of phosphorous acid and hydrochloric acid.
  • the reaction mixture thus obtained is heated to reflux with addition of formaldehyde.
  • the reaction time can vary from 1 to 5 h.
  • the derivatives of the polyaminomethylenephosphonate object of this invention are added to the aqueous systems in quantities between 2 and 50 mg/1 in order to inhibit precipitation, deposition and adhesion of scale, especially CaCO 3 .
  • the expression “inhibits precipitation and formation of deposits” includes threshold effect, dispersion, solubilization or modification of the precipitate's morphology.
  • the expression “inhibits the adhesion” defines just that scale is easily removed e.g. by simple washing/rinsing and not by mechanical or chemical treatment, not being the incrustation strongly bonded to the surface to which it adheres.
  • scale includes incrustation formed by CaCO 3 , CaSO BaSO deposit and can be
  • aqueous systems refers to industrial and/or commercial systems that use water in heat-exchange processes and includes cooling towers, boilers, desalination systems, gas scrubbers; furthermore, processes of desalination by Reverse Osmosis (RO) are included. Of particular importance are systems operating in severe conditions such as high pH and high concentrations of calcite (CaCO 3 ).
  • polyaminomethylenephosphonate derivatives object of the present invention are illustrated in the following examples, which clarify their applications, without however limiting the scope.
  • reaction mixutre was heated at 90° ⁇ 95°C.
  • Ethylene oxide was than added stepwise at such a rate that, with external cooling applied, the temperature did not exceed 100°C.
  • Infrated analysis of the product showed the presence of metfiylenephosphonic amine groups, while P 31 NMR analysis indicate that at least 90% of the amine groups had been phosphonomethylated-
  • the impurities include unreached phosphorous acid, phosphoric acid and other unidentified compounds.
  • Threshold Effect on CaCO at pH 10.
  • T 70°C T lOOppm of CaCOg The method describes the procedure for the determination of theThreshold Effect, that is the
  • This method measures the efficiency of a dispersant by titration of the Calcium ion remaining in a solution supersaturated with C COg respectively before and after treatment in an oven at
  • HEDP Hydroxy-ethylydene-l.l-diphosphonie Acid
  • DTPMP Diethylenetriamine penta (methylenephosphonic acid)
  • PBTC Phosphono Butane tris Carboxylic Acid
  • the Grace "CLOUD POINT TEST" was used for testing the calcium-sensitivity. This simple method allows calcium-sensitivity to be verified visually by estimating the turbidity point of an inhibitor solution in a concentrated calcium solution.
  • the inhibitor is added at increasing amounts to hard water having the following characteristics: 500 ppm of Ca++ ( as CaC ,),
  • pH 8.3 (0.05 M of Boric buffer), at a temperature of 60°C and 100°C for 24 h.
  • the method consists in the addition a known quantity of solution of ferric ions to an aqueous solution of inhibitor at constant pH. After 24 hours under agitation the aspect of the sample is evaluated. The samples where a precipitate is present after 24 hours of agitation are considered " precipitated" and so the first clear sample has been considered in order to attribute a sequestring value.
  • the results obtained are summarised in table 9.
  • Corrosion Inhibition The corrosion of metal equipment is an almost universal problem for aqueous systems: on a metal surface two distinct areas coexist, anode and cathode, which in practice may be situated very close to each other and set up an electrical circuit with consequent Redox reactions leading to the solubilization of the metals. In particular iron surfaces are transformed into water-soluble Fe ions. The corrosion, and therefore the loss of metal from part of the structure, takes place only in the anodic zone.
  • the test lasts 5 days with a constant airflow bubbled through the solution.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Medicinal Chemistry (AREA)
  • Water Supply & Treatment (AREA)
  • General Chemical & Material Sciences (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
  • Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Polyamides (AREA)

Abstract

L'invention concerne une nouvelle classe de dérivés de polyaminophosphonate utiles en tant qu'inhibiteurs de précipitation et d'agents dispersants dans des systèmes aqueux. Ces produits présentent une tolérance totale au calcium et peuvent être employés dans des conditions d'utilisation difficiles dans les domaines de traitement de l'eau et de détergence.
PCT/IT2003/000420 2002-07-31 2003-07-03 Derives de polyaminomethylenephosphonate WO2004011475A1 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
AU2003281668A AU2003281668A1 (en) 2002-07-31 2003-07-03 Polyaminomethylenephos phonate derivatives
EP03741094A EP1525206B1 (fr) 2002-07-31 2003-07-03 Derives de polyaminomethylenephosphonate
US10/522,858 US7087781B2 (en) 2002-07-31 2003-07-03 Polyaminomethylenephos phonate derivatives
AT03741094T ATE441655T1 (de) 2002-07-31 2003-07-03 Polyaminomethylenphosphonat-derivate
DE60329109T DE60329109D1 (en) 2002-07-31 2003-07-03 Polyaminomethylenphosphonat-derivate

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
IT001706A ITMI20021706A1 (it) 2002-07-31 2002-07-31 Poliamminomeilenfosfono derivati.
ITMI2002A001706 2002-07-31

Publications (1)

Publication Number Publication Date
WO2004011475A1 true WO2004011475A1 (fr) 2004-02-05

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PCT/IT2003/000420 WO2004011475A1 (fr) 2002-07-31 2003-07-03 Derives de polyaminomethylenephosphonate

Country Status (8)

Country Link
US (1) US7087781B2 (fr)
EP (1) EP1525206B1 (fr)
AT (1) ATE441655T1 (fr)
AU (1) AU2003281668A1 (fr)
DE (1) DE60329109D1 (fr)
ES (1) ES2332266T3 (fr)
IT (1) ITMI20021706A1 (fr)
WO (1) WO2004011475A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006049824A1 (fr) 2004-10-29 2006-05-11 General Electric Company Nouvelle composition de traitement de metal non chrome
CN101589054A (zh) * 2006-12-11 2009-11-25 塞福斯贸易有限公司 反应性膦酸酯
US7659315B2 (en) * 2004-02-02 2010-02-09 Giovanni Bozzetto S.P.A. Use of polyaminomethylenephosphonates as dispersing agents
EP3970490A1 (fr) 2020-09-16 2022-03-23 Bode Chemie GmbH Désinfectant de surface à adhésivité réduite

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100000579A1 (en) * 2008-07-03 2010-01-07 Reinbold Robert S Compositions And Methods For Removing Scale And Inhibiting Formation Thereof
KR20150068829A (ko) * 2013-12-12 2015-06-22 삼성전자주식회사 알킬 암모늄염 화합물을 포함하는 유도 용질
BE1021535B1 (nl) 2014-01-08 2015-12-09 Eoc Surfactants Nv Nitrosamine inhibitie in tertiair alkylamine oxide samenstellingen
US9765286B2 (en) 2014-12-22 2017-09-19 Ecolab Usa Inc. Warewashing composition containing alkanol amine phosphonate and methods of use

Citations (9)

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GB1392044A (en) * 1971-06-26 1975-04-23 Ciba Geigy Ag Corrosion inhibiting composition
US4085134A (en) * 1974-02-15 1978-04-18 Petrolite Corporation Amino-phosphonic-sulfonic acids
SU643177A1 (ru) * 1977-04-11 1979-01-25 Научно-Производственное Объединение "Энергоцветмет" Состав дл регенерации катионита
US4187245A (en) * 1975-06-02 1980-02-05 Petrolite Corporation Hydroxypropylene-amino-phosphonic-sulfonic acids
EP0282260A2 (fr) * 1987-03-13 1988-09-14 The Dow Chemical Company Procédé pour la prévention de la corrosion et de la formation de tartre par le manganèse dans les systèmes aqueux, à l'aide d'acides aminophosphoniques
GB2244050A (en) * 1990-04-16 1991-11-20 Baker Hughes Inc Metal ion complexes for use as scale inhibitors
EP0479462A1 (fr) * 1990-10-04 1992-04-08 Britoil Plc Procédé antitartre
EP0628518A1 (fr) * 1993-06-14 1994-12-14 Monsanto Europe S.A./N.V. Procédé empêchant la formation des dépôts d'oxalate
WO2001079215A1 (fr) * 2000-04-18 2001-10-25 Dow Global Technologies Inc. Acides n?$g(a),n$g(v)¿-dialkyle aminomethylenephosphoniques et leur utilisation

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US20030216275A1 (en) * 2001-04-18 2003-11-20 Crump Druce K Nª,n -dialkyl aminomethylenephosphonic acids and use thereof

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1392044A (en) * 1971-06-26 1975-04-23 Ciba Geigy Ag Corrosion inhibiting composition
US4085134A (en) * 1974-02-15 1978-04-18 Petrolite Corporation Amino-phosphonic-sulfonic acids
US4187245A (en) * 1975-06-02 1980-02-05 Petrolite Corporation Hydroxypropylene-amino-phosphonic-sulfonic acids
SU643177A1 (ru) * 1977-04-11 1979-01-25 Научно-Производственное Объединение "Энергоцветмет" Состав дл регенерации катионита
EP0282260A2 (fr) * 1987-03-13 1988-09-14 The Dow Chemical Company Procédé pour la prévention de la corrosion et de la formation de tartre par le manganèse dans les systèmes aqueux, à l'aide d'acides aminophosphoniques
GB2244050A (en) * 1990-04-16 1991-11-20 Baker Hughes Inc Metal ion complexes for use as scale inhibitors
EP0479462A1 (fr) * 1990-10-04 1992-04-08 Britoil Plc Procédé antitartre
EP0628518A1 (fr) * 1993-06-14 1994-12-14 Monsanto Europe S.A./N.V. Procédé empêchant la formation des dépôts d'oxalate
WO2001079215A1 (fr) * 2000-04-18 2001-10-25 Dow Global Technologies Inc. Acides n?$g(a),n$g(v)¿-dialkyle aminomethylenephosphoniques et leur utilisation

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CHEMICAL ABSTRACTS, vol. 132, no. 5, 31 January 2000, Columbus, Ohio, US; abstract no. 54509, WANG, RUI ET AL: "(HO)2OPCH2{N[CH2PO(OH)2]CH2CH2}nN[CH2PO(OH)2]2" XP002228000 *
FRIGERIO, M. ET AL: "Sequestering agents in dyeing and printing", TINCTORIA (1987), 84(3), 57-64, 1987, XP008024344 *
SOVIET INVENTIONS ILLUSTRATED Section Ch Week 7941, 21 November 1979 Derwent World Patents Index; Class A91, Page 12, AN 75036b, XP002228001 *
ZHONGGUO FUSHI YU FANGHU XUEBAO (1999), 19(5), 273-279, 1999 *

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7659315B2 (en) * 2004-02-02 2010-02-09 Giovanni Bozzetto S.P.A. Use of polyaminomethylenephosphonates as dispersing agents
WO2006049824A1 (fr) 2004-10-29 2006-05-11 General Electric Company Nouvelle composition de traitement de metal non chrome
AU2005301122B2 (en) * 2004-10-29 2011-07-21 Chemetall Corp. Novel non-chrome metal treatment composition
CN101048435B (zh) * 2004-10-29 2012-05-30 凯麦塔尔公司 新型无铬金属处理组合物
CN101589054A (zh) * 2006-12-11 2009-11-25 塞福斯贸易有限公司 反应性膦酸酯
EP3970490A1 (fr) 2020-09-16 2022-03-23 Bode Chemie GmbH Désinfectant de surface à adhésivité réduite
WO2022058262A1 (fr) 2020-09-16 2022-03-24 Bode Chemie Gmbh Désinfectant de surface ayant un pouvoir collant réduit

Also Published As

Publication number Publication date
ITMI20021706A1 (it) 2004-02-01
EP1525206B1 (fr) 2009-09-02
US20050171376A1 (en) 2005-08-04
EP1525206A1 (fr) 2005-04-27
ATE441655T1 (de) 2009-09-15
DE60329109D1 (en) 2009-10-15
AU2003281668A1 (en) 2004-02-16
US7087781B2 (en) 2006-08-08
ES2332266T3 (es) 2010-02-01

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